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111.
KANG Qiao-xiang YANG Zhi-wang LI Cui-lin MA Heng-chang GUO Zhen WANG You-peng XU Da-hai LEI Zi-qiang 《合成化学》2004,12(Z1)
Oxidation of alcohols to the corresponding aldehydes or ketones is one of the most fundamental reactions in organic chemistry [1,2]. Some of the products of the oxidation exhibit an important role in the organic synthesis as well as pharmaceutical synthesis. In most reactions, the lanthanide complexes show satisfied catalytic activities for some compounds. Furthermore, there has been increasing interest in the lanthanide complexes and several reports have appeared in the literature [3, 4]. But the exploitation of these complexes for the oxidation of some organic substrates has been limited. Here we reported a method for the preparation and the catalytic properties as well as the recycling of lanthanide complexes in oxidation of alcohols.The synthetic procedure for the polymer supported lanthanide complexes is shown as following(scheme 1):●-NH2+CICH2COOH(C2Hs)3N→●-NHCH2COOHM=Ce(Ⅲ), Tb(Ⅲ), Sm(Ⅲ)scheme 1The oxidation of benzyl alcohol was carried out in the presence of iodosylbenzene by the polymer supported Ce(Ⅲ), Tb(Ⅲ) and Sm(Ⅲ) catalysts at 80℃ for 4.0h, the yields of benz-aldehyde are as following (table 1):Table 1 Oxidation of benzyl alcohol with the supported catalysts**Reaction condition: benzyl alcohol 0.1 mmol, iodosylbenzene 0.15mmol,catalyst 0.2mg, 80℃ for 4.0h in 1,2-dichloroethane.It can be seen from the table that the Tb(Ⅲ) complex shows higher catalytic activity for the oxidation of benzyl alcohol. Further investigation is now being carded on to optimize the results. 相似文献
112.
YingChunLIU GuoZhenXIAO QiWANG 《中国化学快报》2004,15(7):879-882
The diffusivity and viscosity of water confined in micropores were studied by molecular dynamics simulations. The effects of pore width and density were analyzed at pore widths from 0.9 to 2.6nm. The diffusivity in micropores is lower than that of the bulk, and it decreases as pore width decreases and as density increases. But the viscosity in micropores is much larger than that of the bulk, and it increases as pore width decreases and as density increases. The diffusivity in channel parallel direction is obviously larger than that in channel perpendicular directions. 相似文献
113.
Affinity probe capillary isoelectric focusing (CIEF) with laser-induced fluorescence was explored for detection of Ras-like G proteins. In the assay, a fluorescent BODIPY FL GTP analogue (BGTPgammaS) and G protein were incubated resulting in formation of BGTPgammaS-G protein complex. Excess BGTPgammaS was separated from BGTPgammaS-G protein complex by CIEF using a 3-10 pH gradient and detected in whole-column imaging mode. In other cases, a single point detector was used to detect zones during the focusing step of CIEF using a 2.5-5 pH gradient. In this case, analyte peaks passed the detector in approximately 5 min at an electric field of 350 V/cm. Detection during focusing allowed for more reproducible assays at shorter times but with a sacrifice in sensitivity compared to detection during mobilization. Resolution was adequate to separate BGTPgammaS-Ras and BGTPgammaS-Rab3A complexes. Formation of specific complexes was confirmed by adding GTPgammaS to samples containing BGTPgammaS-G protein. GTPgammaS competed with BGTPgammaS for G protein binding sites resulting in decreased BGTPgammaS-G protein peak heights. The concentrating effect of CIEF enabled detection limits of 30 pM. 相似文献
114.
A multimode Holstein Hamiltonian is used to describe optical excitations in quaterthiophene pinwheel aggregates. The Hamiltonian includes the coupling of excitons originating from the 1A(g)-->1B(u) electronic transition to phonons originating from the five intramolecular vibrational modes known from oligothiophene solution absorption/emission spectroscopy. The resulting eigenstates with lowest energy are best described as hybrid polaron phonons. The polarons are formed by coupling excitons with the higher frequency (688, 1235, and 1551 cm(-1)) vibrational modes, while the (optical) phonons arise from the lower frequency (161 and 333 cm(-1)) modes. The polaron phonons are responsible for the fine structure defining the A(1) band in the low-energy region of the absorption spectrum, ranging from the band origin to approximately 1500 cm(-1) beyond. The calculated A(1) band of quaterthiophene aggregates agrees favorably with that observed from thin films. 相似文献
115.
Zhen‐Feng Zhang Dong‐Chao Wang Jian‐Ge Wang Gui‐Rong Qu 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(9):o524-o527
The molecules of 2,2,2‐trichloro‐N,N′‐diphenylethane‐1,1‐diamine, C14H13Cl3N2, are linked into (040) sheets by a combination of C—H...Cl and C—H...π(arene) hydrogen bonds. In 2,2,2‐trichloro‐N,N′‐bis(4‐methylphenyl)ethane‐1,1‐diamine, C16H17Cl3N2, the molecules are linked into C(7) chains by two independent C—H...Cl hydrogen bonds and one Cl...Cl contact. 相似文献
116.
Honying M Han H Qiao C Richardson NV Yue W Jianhua Z Haiyang L Pimo H Shining B 《The Journal of chemical physics》2004,121(14):6972-6977
The structure of perylene adsorbed on Ru(0001) surface has been studied by ultraviolet photoemission spectroscopy (UPS) and low-energy electron diffraction. An ordered p(4x4) structure is observed from a monolayer (about 4 A thickness) of the perylene on Ru(0001) surface. UPS measurements show the molecular features, from the perylene multiplayer, between 2 and 10 eV below the Fermi level. Angle-resolved ultraviolet photoemission spectroscopy measurements suggest that the perylene molecular plane is parallel to the substrate. Temperature dependent UPS measurements show that the perylene multilayer is stable on Ru(0001) surface up to 125 degrees C. The desorption of the multilayer and the decomposition of the monolayer are observed above 125 degrees C. 相似文献
117.
Zhen G Eggli V Vörös J Zammaretti P Textor M Glockshuber R Kuennemann E 《Langmuir : the ACS journal of surfaces and colloids》2004,20(24):10464-10473
Understanding the conformation, orientation, and specific activity of proteins bound to surfaces is crucial for the development and optimization of highly specific and sensitive biosensors. In this study, the very efficient enzyme beta-lactamase is used as a model protein. The wild-type form was genetically engineered by site-directed mutagenesis to introduce single cysteine residues on the surface of the enzyme. The cysteine thiol group is subsequently biotinylated with a dithiothreitol (DTT)-cleavable biotinylation reagent. beta-Lactamase is then immobilized site-specifically via the biotin group on neutral avidin-covered surfaces with the aim to control the orientation of the enzyme molecule at the surface and study its effect on enzymatic activity using Nitrocefin as the substrate. The DTT-cleavable spacer allows the release of the specifically bound enzyme from the surface. Immobilization of the enzyme is performed on a monolayer of the polycationic, biotinylated polymer PLL-g-PEG/PEG-biotin assembled on niobium oxide (Nb2O5) surfaces via neutral avidin as the docking site. Two different assembly protocols, the sequential adsorption of avidin and biotinylated beta-lactamase and the immobilization of preformed complexes of beta-lactamase and avidin, are compared in terms of immobilization efficiency. In situ optical waveguide lightmode spectroscopy and colorimetric analysis of enzymatic activity were used to distinguish between specific and unspecific enzyme adsorption, to sense quantitatively the amount of immobilized enzyme, and to determine Michaelis-Menten kinetics. All tested enzyme variants turned out to be active upon immobilization at the polymeric surface. However, the efficiency of immobilized enzymes relative to the soluble enzymes was reduced about sevenfold, mainly because of impaired substrate (Nitrocefin) diffusion or restricted accessibility of the active site. No significant effect of different enzyme orientations could be detected, probably because the enzymes were attached to the surface through long, flexible PEG chain linkers. 相似文献
118.
Rafael D. Sorkin Robert M. Wald Zhang Zhen Jiu 《General Relativity and Gravitation》1981,13(12):1127-1146
We examine the entropy of self-gravitating radiation confined to a spherical box of radiusR in the context of general relativity. We expect that configurations (i.e., initial data) which extremize total entropy will be spherically symmetric, time symmetric distributions of radiation in local thermodynamic equilibrium. Assuming this is the case, we prove that extrema ofS coincide precisely with static equilibrium configurations of the radiation fluid. Furthermore, dynamically stable equilibrium configurations are shown to coincide with local maxima ofS. The equilibrium configurations and their entropies are calculated and their properties are discussed. However, it is shown that entropies higher than these local extrema can be achieved and, indeed, arbitrarily high entropies can be attained by configurations inside of or outside but arbitrarily near their own Schwarzschild radius. However, if we limit consideration to configurations which are outside their own Schwarzschild radius by at least one radiation wavelength, then the entropy is bounded and we find Smax MR, whereM is the total mass. This supports the validity for self-gravitating systems of the Bekenstein upper limit on the entropy to energy ratio of material bodies. 相似文献
119.
为探究稀土氧化物中氟(F)和氯(Cl)元素含量的快速检测方法,通过全自动高温水解仪对氧化镧铈样品进行前处理,并利用氢氧根体系离子色谱仪检测吸收液中F-、Cl-离子的含量,建立了基于全自动高温水解-离子色谱法测定氧化镧铈中的F、Cl元素含量的快速检测方法,该方法有效避免了传统前处理方法过程复杂、分析时间慢、极易受人为干扰的问题。称取0.3g氧化镧铈样品,在氧气流量为300 mL/min,1100 ℃高温下水解燃烧20 min,吸收定容为体积20mL的吸收液,以NAOH(15mmol/L)作为淋洗液,经色谱柱分离,测得F-与Cl-在质量浓度为1.00 mg/L-15.00 mg/L范围内,质量浓度与离子色谱峰面积呈线性关系,相关系数均为0.9999。检出限分别为0.003mg/L和0.12mg/L。全自动高温水解仪联用离子色谱仪检测系统对氧化镧铈中F-的平均加标回收率测定结果为98.4%,标准偏差RSD为0.94%;对Cl-的加标回收率测定结果为97.8%,RSD为2.86%。说明该方法较高准确度及精密度,测试结果准确可靠满足企业和检测机构的测试需求,为稀土氧化中氟、氯元素含量的研究及相关产品的开发提供了理论基础。 相似文献
120.